CN116751225A - Preparation method of long-chain sulfur bridge type reverse ester methyl tin mercaptide - Google Patents
Preparation method of long-chain sulfur bridge type reverse ester methyl tin mercaptide Download PDFInfo
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- CN116751225A CN116751225A CN202311033884.6A CN202311033884A CN116751225A CN 116751225 A CN116751225 A CN 116751225A CN 202311033884 A CN202311033884 A CN 202311033884A CN 116751225 A CN116751225 A CN 116751225A
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
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Abstract
The invention belongs to the technical field of tin-containing acyclic compounds, and particularly relates to a preparation method of long-chain sulfur bridge type reverse ester methyl tin mercaptide. Carrying out condensation reaction on a methyl tin trichloride aqueous solution and mercaptoethyl oleate, and then adding an acid binding agent to obtain a reaction solution; adding dithiol type sulfur bridging agent into the reaction liquid to carry out bridging reaction, regulating pH, standing and layering to obtain an oil phase, and carrying out vacuum dehydration on the oil phase to obtain long-chain sulfur bridge type reverse ester methyl tin mercaptide. The invention solves the defect of the traditional sulfur bridge type reverse ester thiol methyl tin, on the premise of ensuring high thermal stability, on one hand, the preparation time of the long-chain sulfur bridge type reverse ester thiol methyl tin can be obviously shortened, the longer molecular chain can obviously improve the compatibility of the sulfur bridge type reverse ester thiol methyl tin and PVC, on the other hand, the Sn content can be obviously reduced, and the production cost is reduced.
Description
Technical Field
The invention belongs to the technical field of tin-containing acyclic compounds, and particularly relates to a preparation method of long-chain sulfur bridge type reverse ester methyl tin mercaptide.
Background
Polyvinyl chloride (PVC) is the most widely used plastic with the greatest worldwide yield, and can be widely used for pipes, wires and cables, packaging films, bottles, foaming materials, sealing materials, etc. However, the PVC resin has the defect of active chlorine atom structure, so that the heat stability of the PVC resin is difficult to be satisfied, especially under the high-temperature and high-shear processing conditions, HCl is easy to remove, the removal of Cl atoms can be further promoted by the generated HCl, a C=C double bond structure is formed, the color of the PVC product is deepened, the mechanical property is reduced, and the service life is seriously influenced.
The heat stabilizer is an important auxiliary agent for inhibiting PVC degradation and improving the heat stability of PVC. Common heat stabilizers include lead salts, calcium and zinc, and organotin, among others. The lead salt heat stabilizer has good heat stability, but the lead salt is toxic, so that the application of the lead salt heat stabilizer in PVC products which can be contacted with food is limited; the calcium zinc thermal stability has better lubricity and initial stability, but the disadvantages of zinc burning, easy precipitation, poor transparency, poor long-term stability and the like are generally existed. Methyl tin mercaptide is the most representative product in organic tin heat stabilizers, has the advantages of excellent long-term heat stability, weather resistance, transparency, compatibility, fluidity and the like, and is regarded as a nontoxic and safe heat stabilizer variety. However, methyl tin mercaptide has poor lubricity and requires additional additives to prevent sticking during PVC hot working; the raw material tin has high price, so that the preparation cost is high; in addition, the heat stability of the material in the fields of pipes, tubes and profiles is limited greatly.
For this reason, the development of novel organotin compounds of high molecular weight can effectively avoid the disadvantages of the conventional methyl tin mercaptide. The sulfur bridge type reverse ester tin is novel organic tin, the high molecular weight of the novel organic tin not only increases compatibility and partial lubricity, but also reduces the consumption of tin atoms, and the production cost is obviously reduced.
Chinese patent CN 102516289a discloses a method for preparing sulfur bridge-containing reverse ester methyl tin mercaptide, which comprises the steps of simultaneously dripping a monomethyl tin trichloride aqueous solution and a sodium sulfide sulfur bridging agent aqueous solution into mercaptoethanol oleate, so that the condensation reaction and the sulfur bridging reaction are simultaneously carried out, and adjusting the pH by ammonia water, thereby obtaining the sulfur bridge-containing reverse ester methyl tin mercaptide under control. Chinese patent CN102584889A discloses a thio (joint) reverse ester tin, a preparation method and application, wherein the method comprises the steps of uniformly mixing mercaptoethanol oleate, monomethyl tin trichloride and water, adding part of ammonia water, adding an inorganic sulfide salt sulfur bridge agent, adjusting pH by the ammonia water, washing by water and dehydrating. However, in the two patents, the sulfur bridge type reverse ester tin production processes adopt inorganic sulfur salt sulfur bridge agent, and high-toxicity hydrogen sulfide is generated in the reaction process, so that the requirements of environmental protection and safety are not met; moreover, the inorganic salt sulfur bridging agent has low reaction activity, and is difficult to effectively bridge tin reverse ester; in addition, the sulfur bridge bonds are connected in a 'Sn-S-Sn' structure, so that the rigidity is high, and the lubricity of the organic tin is difficult to effectively improve.
Disclosure of Invention
The invention aims to provide a preparation method of long-chain sulfur bridge type reverse ester thiol methyl tin, which solves the defects of the traditional sulfur bridge type reverse ester thiol methyl tin, on the premise of ensuring high thermal stability, can obviously shorten the preparation time of the long-chain sulfur bridge type reverse ester thiol methyl tin, obviously improve the compatibility of the sulfur bridge type reverse ester thiol methyl tin and PVC through a longer molecular chain, and on the other hand, can obviously reduce the Sn content and reduce the production cost.
The preparation method of the long-chain sulfur bridge type reverse ester methyl tin mercaptide comprises the steps of carrying out condensation reaction on a monomethyl tin trichloride aqueous solution and mercaptoethyl oleate, and then adding an acid binding agent to obtain a reaction solution; adding dithiol type sulfur bridging agent into the reaction liquid to carry out bridging reaction, regulating pH, standing and layering to obtain an oil phase, and carrying out vacuum dehydration on the oil phase to obtain long-chain sulfur bridge type reverse ester methyl tin mercaptide.
The dithiol type sulfur bridge agent is one of 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1, 7-heptanedithiol, 1, 8-octanedithiol, 1, 9-nonanedithiol or 1, 10-decanedithiol.
The mass concentration of the monomethyl tin trichloride aqueous solution is 40-60wt.%.
The mol ratio of the chlorine atoms in the mercaptoethyl oleate to the monomethyl stannic trichloride aqueous solution to the acid binding agent is 1:1.1-1.5:1.0-1.2.
The acid binding agent is ammonia water or sodium hydroxide.
The condensation reaction temperature is 30-50 ℃, and the condensation reaction time is 0.5-1h.
The mole ratio of the dithiol type sulfur bridging agent to chlorine atoms in the monomethyl tin trichloride aqueous solution is 0.09-0.35.
The bridging reaction temperature is 30-50 ℃, and the bridging reaction time is 0.5-1h.
The pH is adjusted to 3-6 by adding sodium hydroxide solution.
The vacuum dehydration pressure is-0.08-0.1 Mpa, and the vacuum dehydration temperature is 90-120 ℃.
The principle of the invention is shown in formulas (1) and (2), wherein the mercapto group of mercaptoethyl oleate reacts with part of chlorine atoms in monomethyl tin trichloride, and then an acid binding agent reacts with generated HCl to ensure the condensation reaction. Then, the generated monomethyl dioleate reverse ester stannic chloride and dithiol sulfur bridging agent undergo a bridging reaction, and the pH is regulated by dropwise adding sodium hydroxide, namely, HCl generated by the bridging reaction is neutralized, so that the smooth proceeding of the bridging reaction is ensured. Compared with the traditional inorganic sulfide sulfur bridging agent, the disulfide bridge agent can form a long-chain sulfur bridge structure of Sn-S-R-S-Sn, so that the bridging reaction activity can be improved, the reaction time is reduced, the Sn-S-Sn rigid structure generated by the inorganic sulfide sulfur bridging agent is avoided, the Sn atom utilization rate is obviously improved, and the lubricity of the sulfur bridge type heat stabilizer is improved.
In the formulas (1) and (2), R 1 Is octyl;
R 2 is a heptyl group;
r is (-CH) 2 -） n N=2, 3, 5, 6, 7, 8, 9 or 10.
The beneficial effects of the invention are as follows:
(1) Compared with sulfur bridge type reverse ester methyl tin mercaptide prepared by inorganic sulfur salt sulfur bridging agent, the invention adopts organic dithiol as the sulfur bridging agent, avoids the risk of releasing highly toxic hydrogen sulfide when inorganic sulfur salt is prepared into aqueous solution or in bridging reaction, and is a green and environment-friendly method;
(2) Compared with the existing sodium sulfide sulfur bridging agent, on one hand, the organic dithiol sulfur bridging agent is more beneficial to being dissolved in the oil phase monomethyl dioleate reverse ester stannic chloride intermediate product, and the sodium sulfide sulfur bridging agent has higher solubility in the water phase, so that the contact probability with the intermediate product can be obviously improved by adopting the organic dithiol sulfur bridging agent, the reactivity of the bridging reaction is improved, and the reaction time is shortened; on the other hand, the organic dithiol sulfur bridging agent solves the problems of emulsification and the like caused by the alkaline environment formed by the dissolution of sodium sulfide in water when the sodium sulfide sulfur bridging agent is adopted in the production process;
(3) The sulfur bridge in the product of the invention is of a long chain structure of Sn-S-R-S-Sn, and organic molecular chains exist in the sulfur bridge, which has a longer organic chain than the Sn-S-Sn sulfur bridge bond formed by the sodium sulfide sulfur bridge agent, thus not only reducing the structural rigidity, but also improving the compatibility with PVC, thereby weakening the cohesive force among PVC polymer molecules and improving the lubricity.
(4) Compared with inorganic S-Sn-S sulfur bridge bonds, the long-chain organic Sn-S-R-S-Sn sulfur bridge bonds have longer molecular chains, the Sn content is obviously reduced along with the growth of R carbon chains, and the long-chain organic sulfur bridge products have higher thermal stability under the same dosage as inorganic sulfur bridge products, so that the utilization rate of Sn atoms is improved, and the market competitiveness of the products is improved.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the product of example 1.
FIG. 2 is a nuclear magnetic resonance carbon spectrum of the product of example 1.
Fig. 3 is a graph of yellow index results.
FIG. 4 is a graph of the results of a two-roll dynamic thermal stability test.
Fig. 5 is a graph of torque rheology experimental results.
Detailed Description
The invention is further described below with reference to examples.
Example 1
250g of monomethyl tin trichloride aqueous solution with the mass fraction of 60wt.% and 430g of mercaptoethyl oleate are placed in a 2000ml three-neck flask, condensation reaction is carried out for 0.5h at 30 ℃, and then 85.5g of ammonia water with the mass fraction of 25wt.% is gradually added dropwise; after the completion of the dropwise addition, 58.5g of 1, 2-ethanedithiol was added to the reaction solution, and the reaction was bridged at 30℃for 0.5 hours, followed by dropwise addition of 124.3g of an aqueous sodium hydroxide solution having a mass fraction of 20wt.%, and the pH of the reaction solution was controlled to 6.0. After standing and layering, separating out an oil phase, and dehydrating for 2 hours at 90 ℃ and a vacuum degree of-0.08 MPa to obtain 715.0g of a product, wherein the yield is 99.3%, the Sn content is 13.4% and the S content is 11.1%. The nuclear magnetic resonance hydrogen spectrum of the product is shown in figure 1, and the nuclear magnetic resonance carbon spectrum of the product is shown in figure 2.
Example 2
300g of monomethyl tin trichloride aqueous solution with the mass fraction of 50wt.% and 460g of mercaptoethyl oleate are placed in a 2000ml three-neck flask, condensation reaction is carried out for 0.75h at 50 ℃, and then 322.8g of sodium hydroxide solution with the mass fraction of 20wt.% is gradually added dropwise; after the completion of the dropwise addition, 28.6g of 1, 3-propanedithiol was added to the above reaction solution, and the bridging reaction was carried out at 50℃for 0.75 hours, followed by dropwise addition of 53.0g of an aqueous sodium hydroxide solution having a mass fraction of 20wt.%, and the pH of the reaction solution was controlled to 5.0. After standing and layering, separating out an oil phase, and dehydrating for 2 hours at 120 ℃ and a vacuum degree of-0.09 MPa to obtain 711.5g of a product, wherein the yield is 98.8%, the Sn content is 13.3% and the S content is 11.0%.
Example 3
300g of monomethyl tin trichloride aqueous solution with the mass fraction of 50wt.% and 430g of mercaptoethyl oleate are placed in a 2000ml three-neck flask, condensation reaction is carried out for 0.5h at 50 ℃, and then 251.5g of sodium hydroxide solution with the mass fraction of 20wt.% is gradually added dropwise; after the completion of the dropwise addition, 84.7g of 1, 5-pentanedithiol was added to the above reaction solution, and the reaction was bridged at 50℃for 1 hour, followed by dropwise addition of 124.3g of an aqueous sodium hydroxide solution having a mass fraction of 20wt.%, and the pH of the reaction solution was controlled to 5.0. After standing and layering, separating out an oil phase, and dehydrating for 2 hours at 120 ℃ and a vacuum degree of-0.09 MPa to obtain 740.1g of a product, wherein the yield is 99.2%, the Sn content is 13.1% and the S content is 10.8%.
Example 4
300g of monomethyl tin trichloride aqueous solution with the mass fraction of 50wt.% and 500g of mercaptoethyl oleate are placed in a 2000ml three-neck flask, condensation reaction is carried out for 1h at 40 ℃, and then 321.6g of sodium hydroxide solution with the mass fraction of 20wt.% is gradually added dropwise; after the completion of the dropwise addition, 40.7g of 1, 6-hexanedithiol was added to the above reaction solution, and the bridging reaction was carried out at 40℃for 0.5 hours, followed by dropwise addition of 54.1g of an aqueous solution of sodium hydroxide having a mass fraction of 20wt.%, and the pH of the reaction solution was controlled to 3.0. After standing and layering, separating out an oil phase, and dehydrating for 2 hours at 100 ℃ under the vacuum degree of-0.09 MPa to obtain 765.1g of a product, wherein the yield is 99.1%, the Sn content is 13.0% and the S content is 10.7%.
Example 5
375g of a 40wt.% aqueous solution of monomethyl tin trichloride and 520g of mercaptoethyl oleate are placed in a 2000ml three-neck flask, subjected to condensation reaction at 40 ℃ for 0.5h, and then 304.1g of a 20wt.% sodium hydroxide solution is gradually added dropwise; after the completion of the dropwise addition, 58.9g of 1, 7-heptanediol was added to the above reaction solution, and the reaction was bridged at 40℃for 1 hour, followed by dropwise addition of 71.7g of an aqueous sodium hydroxide solution having a mass fraction of 20wt.%, and controlling the pH of the reaction solution to 4.0. After standing and layering, separating out an oil phase, and dehydrating for 2 hours at 100 ℃ under the vacuum degree of-0.1 MPa to obtain 797.3g of a product, wherein the yield is 98.4%, the Sn content is 12.9% and the S content is 10.6%.
Example 6
300g of monomethyl tin trichloride aqueous solution with the mass fraction of 50wt.% and 540g of mercaptoethyl oleate are placed in a 2000ml three-neck flask, condensation reaction is carried out for 0.5h at 40 ℃, and then 315.8g of sodium hydroxide solution with the mass fraction of 20wt.% is gradually added dropwise; after the completion of the dropwise addition, 53.5g of 1, 8-octanedithiol was added to the reaction solution, and the reaction was bridged at 40℃for 0.5 hours, followed by dropwise addition of 60.0g of a 20wt.% aqueous sodium hydroxide solution, and the pH of the reaction solution was controlled to 6.0. After standing and layering, separating out an oil phase, and dehydrating for 2 hours at 100 ℃ and a vacuum degree of-0.1 MPa to obtain a product 806.8 g with a yield of 97.8%, a Sn content of 12.5% and a S content of 10.4%.
Example 7
300g of a 50wt.% aqueous solution of monomethyl tin trichloride and 560g of mercaptoethyl oleate are placed in a 2000ml three-neck flask, subjected to condensation reaction at 40 ℃ for 0.5h, and then 327.5g of a 20wt.% sodium hydroxide solution is gradually added dropwise; after the completion of the dropwise addition, 46.5g of 1, 9-nonyldithiol was added to the above reaction solution, and the reaction was bridged at 40℃for 0.5 hours, followed by dropwise addition of 48.3g of an aqueous sodium hydroxide solution having a mass fraction of 20wt.%, and the pH of the reaction solution was controlled to 6.0. After standing and layering, separating out an oil phase, and dehydrating for 2 hours at 100 ℃ under the vacuum degree of-0.1 MPa to obtain 817.7g of a product, wherein the yield is 97.6%, the Sn content is 12.3% and the S content is 10.3%.
Example 8
300g of 50wt.% of monomethyl tin trichloride aqueous solution and 580g of mercaptoethyl oleate are placed in a 2000ml three-neck flask, subjected to condensation reaction at 40 ℃ for 0.5h, and then 339.2g of 20wt.% sodium hydroxide solution is gradually added dropwise; after the completion of the dropwise addition, 37.8g of 1, 10-decanedithiol was added to the above-mentioned reaction solution, and the bridging reaction was carried out at 40℃for 0.5 hours, and 36.6g of an aqueous sodium hydroxide solution having a mass fraction of 20wt.% was further added dropwise, whereby the pH of the reaction solution was controlled to 6.0. After standing and layering, separating out an oil phase, and dehydrating for 2 hours at 100 ℃ under the vacuum degree of-0.1 MPa to obtain 828.8g of a product, wherein the yield is 97.6%, the Sn content is 12.2% and the S content is 10.1%.
Comparative example 1
Referring to the method of Chinese patent CN102584889A, 430g of mercaptoethyl oleate and 300g of monomethyl tin trichloride aqueous solution with the mass fraction of 50wt.% are added into a 2000ml three-necked round bottom flask, condensation reaction is carried out for 1h at 30 ℃, and then 83.5g of ammonia water with the mass fraction of 25wt.% are gradually added dropwise; after the dripping is finished, 40.9g of ammonia sulfide is added, 130.2g of sodium hydroxide aqueous solution with the mass fraction of 20wt.% is added dropwise, the pH of the reaction solution is controlled to be 6.0, and the bridging reaction is carried out for 1.5 hours at the reaction temperature of about 40 ℃; after standing and layering, separating out an oil phase, dehydrating for 2 hours at 90 ℃ and the vacuum degree of minus 0.08MPa, and finally vacuumizing and dehydrating to obtain 650.2g of product with 96.3 percent of yield, 14.3 percent of Sn and 9.51 percent of S.
The product specifications for examples 1-8 and comparative example 1 are shown in Table 1.
As is clear from Table 1, the preparation methods of long-chain sulfur-bridged reverse ester tin mercaptides of examples 1 to 8 require less total time for the condensation reaction and the bridging reaction, have a low Sn content and have a high S content, as compared with the conventional preparation method of sulfur-bridged reverse ester tin mercaptides of comparative example 1. And the Sn content is reduced, so that the utilization rate of Sn atoms can be improved, the production cost is reduced, and the market competitiveness is improved. The high content of S can decompose the hydroperoxide generated in the PVC thermal processing, reduce the concentration of free radicals, prevent PVC from pyrolysis and aging, assist Sn atoms and improve the thermal stability.
Double-roller dynamic thermal stability experiment and torque rheology experiment:
the raw material formulas of the two-roll dynamic thermal stability test and the torque rheology test are shown in table 2. 100 parts of PVC powder, 1.5 parts of ACR impact modifier, 3.3 parts of dioctyl DOP phthalate, 0.5 part of 70S fatty acid and polyol oligomerization complex ester, 1.0 part of G16 internal lubricant and 1.0 part of heat stabilizer are mixed, and then are respectively placed in a two-roll open mill and a torque rheometer, and a two-roll dynamic thermal stability experiment and a torque rheometer experiment are carried out at 195 ℃. In the experimental process, sample pieces are taken at intervals of 3min, and the samples are sampled by a yellow index meter to measure the yellow index and compare the thermal stability.
FIG. 3 is a graph of the results of yellow index measured after sample pieces are taken at intervals. As can be seen from fig. 3, when the heat stabilizer of example 1 or comparative example 1 was used for the experiment, the yellowness index of the sample piece increased with the increase in kneading time, and the larger the yellowness index was indicative of the more yellow of the sample piece. However, at the same time, the yellowness index of the sample pieces prepared with the heat stabilizer of example 1 was significantly smaller than that of the sample pieces prepared with the heat stabilizer of comparative example 1, which confirmed that the long-chain sulfur-bridged type reverse ester methyl tin mercaptide obtained in example 1 had higher heat stability.
FIG. 4 is a graph showing the results of two-roll dynamic thermal stability test with sample pieces taken at intervals, and it can be seen from FIG. 4 that the sample pieces obtained from the heat stabilizer of example 1 are relatively light in color for the first 15 minutes. After the time had been prolonged to 18 minutes, the sample piece was lighter in color than the heat stabilizer of comparative example 1, although the color was blackened. The above results demonstrate that the long chain sulfur bridge type reverse ester methyl tin mercaptide of example 1 has higher thermal stability.
Fig. 5 is a graph of torque rheology experimental results. From the 0s addition, similar peak and minimum torque occurred for example 1 and comparative example 1, however, the maximum torque for the addition of the heat stabilizer of example 1 was less than the maximum torque for the addition of the heat stabilizer of comparative example 1, indicating that the long chain sulfur bridge type reverse ester methyl tin mercaptide of example 1 had better internal lubricity. The balance torque of the PVC after the heat stabilizer of example 1 is smaller than that after the heat stabilizer of comparative example 1 is added, which further illustrates that the long-chain sulfur bridge type reverse ester thiol methyl tin of example 1 can reduce the viscosity of PVC melt, increase the fluidity, i.e. increase the lubricity.
Claims (10)
1. A preparation method of long-chain sulfur bridge type reverse ester methyl tin mercaptide is characterized in that a monomethyl tin trichloride aqueous solution and mercaptoethyl oleate undergo a condensation reaction, and then an acid binding agent is added to obtain a reaction solution; adding dithiol type sulfur bridging agent into the reaction liquid to carry out bridging reaction, regulating pH, standing and layering to obtain an oil phase, and carrying out vacuum dehydration on the oil phase to obtain long-chain sulfur bridge type reverse ester methyl tin mercaptide.
2. The method for preparing long-chain sulfur bridge type reverse ester thiol methyl tin according to claim 1, wherein the dithiol type sulfur bridge agent is one of 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1, 7-heptanedithiol, 1, 8-octanedithiol, 1, 9-nonanedithiol or 1, 10-decanedithiol.
3. The method for preparing long-chain sulfur bridge type reverse ester methyl tin mercaptide according to claim 1, wherein the mass concentration of the aqueous solution of the monomethyl tin trichloride is 40-60wt.%.
4. The method for preparing long-chain sulfur bridge type reverse ester methyl tin mercaptide according to claim 1, which is characterized in that the mol ratio of chlorine atoms in the aqueous solution of mercaptoethyl oleate and monomethyl tin trichloride to acid binding agents is 1:1.1-1.5:1.0-1.2.
5. The method for preparing long-chain sulfur bridge type reverse ester methyl tin mercaptide according to claim 1, wherein the acid binding agent is ammonia water or sodium hydroxide.
6. The method for preparing long-chain sulfur bridge type reverse ester methyl tin mercaptide according to claim 1, wherein the condensation reaction temperature is 30-50 ℃ and the condensation reaction time is 0.5-1h.
7. The method for preparing long-chain sulfur bridge type reverse ester methyl tin mercaptide according to claim 1, wherein the molar ratio of the dithiol type sulfur bridge agent to chlorine atoms in the monomethyl tin trichloride aqueous solution is 0.09-0.35.
8. The method for preparing long-chain sulfur bridge type reverse ester methyl tin mercaptide according to claim 1, wherein the bridging reaction temperature is 30-50 ℃ and the bridging reaction time is 0.5-1h.
9. The method for preparing long-chain sulfur bridge type reverse ester methyl tin mercaptide according to claim 1, wherein the pH adjustment is carried out by adding sodium hydroxide solution to adjust the pH to 3-6.
10. The method for preparing long-chain sulfur bridge type reverse ester methyl tin mercaptide according to claim 1, wherein the vacuum dehydration pressure is-0.08-0.1 Mpa, and the vacuum dehydration temperature is 90-120 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3979359A (en) * | 1974-11-15 | 1976-09-07 | Cincinnati Milacron Chemicals, Inc. | Carbofunctional sulfur and carboxylate bridged tin compounds |
| CN102304145A (en) * | 2011-07-22 | 2012-01-04 | 浙江海普顿新材料股份有限公司 | Methyl tin reverse thioester and preparation method thereof |
| CN102516289A (en) * | 2011-11-22 | 2012-06-27 | 湖北南星化工总厂 | Preparation method of sulfur bridge-containing reverse ester thiol methyltin |
-
2023
- 2023-08-17 CN CN202311033884.6A patent/CN116751225A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3979359A (en) * | 1974-11-15 | 1976-09-07 | Cincinnati Milacron Chemicals, Inc. | Carbofunctional sulfur and carboxylate bridged tin compounds |
| CN102304145A (en) * | 2011-07-22 | 2012-01-04 | 浙江海普顿新材料股份有限公司 | Methyl tin reverse thioester and preparation method thereof |
| CN102516289A (en) * | 2011-11-22 | 2012-06-27 | 湖北南星化工总厂 | Preparation method of sulfur bridge-containing reverse ester thiol methyltin |
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